PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side struck two times in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen seasons.
